Preparation of chitosan‐g‐poly(acrylamide)/montmorillonite superabsorbent polymer composites: Studies on swelling,thermal, and antibacterial properties

Superabsorbent composites based on chitosan‐g‐poly(acrylamide) and montorillonite (CTS‐g‐PAAm/MMT) were synthesized through in situ radical polymerization by grafting of crosslinked acrylamide onto chitosan backbone in presence of MMT at different contents. The formation of the grafted network was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). The obtained porous structure was observed by scanning electron microscope (SEM). The presence of clay and its interaction with chitosan‐g‐poly(acrylamide) (CTS‐g‐PAAm) matrix was evidenced by ATR‐FTIR analysis. The morphology was investigated by both X‐ray diffraction (XRD) and SEM analyses. It was suggested the formation of mostly exfoliated structures with more porous structures. Besides, the thermal stability of these composites, observed by TGA analysis, was slightly affected by the clay loading as compared to the matrix. These hydrogel composites were also hydrolyzed to achieve anionic hydrogels with ampholytic properties. Swelling behaviors were examined in doubly distilled water, 0.9 wt % NaCl solution and buffer solutions. The water absorbency of all superabsorbent composites was enhanced by adding clay, where the maximum was reached at 5 wt % of MMT. Their hydrolysis has not only greatly optimized their absorption capacity but also improved their swelling rate and salt‐resistant ability. The hydrolyzed superabsorbent showed better pH‐sensitivity than the unhydrolyzed counterparts. The results of the antibacterial activity of these superabsorbents composites against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), assayed by the inhibitory zone tests, have showed moderate inhibition of the bacteria growth. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39747.     

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Copolymerizations of methyl methacrylate (MMA) with 4‐vinylpyridine (4VP) were performed from different monomer feed ratios in 1,4‐dioxan at 30°C under free radical initiation experimental conditions, using Ni(II)α‐Benzoinoxime complex as initiator. The obtained copolymers (PMMA4VP) were examined by FTIR and ¹H NMR spectroscopies. The composition of these copolymers was calculated, using ¹H NMR spectra and elemental analysis. Monomer reactivity ratios were estimated from Fineman–Ross (FR, r_m = 0.550, r_v = 1.165) and Kelen–Tudos (KT, r_m = 0.559, r_v = 1.286) linearization methods, as well as nonlinear error in variables model (EVM) method using the RREVM computer program (RREVM, r_m = 0.559, r_v = 1.264). These values suggest that MMA‐4VP pair copolymerizes randomly. ¹H NMR spectra provide information about the stereochemistry of the copolymers in terms of sequence distributions and configurations. These results showed that the age of the Ni complex has an impact not only on its activity towards polymerization reactions but also on the features of the corresponding copolymers, whereas the chemical composition was insensitive to this prominent factor. The mechanism of MMA‐4VP copolymerization is consistent with a radical process as supported by microstructure and molecular weight distribution studies. Thermal behaviours of these copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

N-3 Polyunsaturated Fatty Acids Modulate In-Vitro T Cell Function in Type I Diabetic Patients

In this work, we assessed the in-vitro effects of eicosapentaenoic acid (EPA; C20:5n-3) and docosahexaenoic acid (DHA; C22:6n-3) (final concentration, 15 microM) on T cell blastogenesis, interleukin-2 and -4 (IL-2, IL-4) secretion, fatty acid composition and intracellular oxidative status in type I diabetic patients with or without complications. Con A stimulated lymphocyte proliferation, glucose uptake, intracellular reduced glutathione levels and catalase activity were lower in diabetics as compared to controls, regardless to the presence of complications. EPA and DHA diminished T-lymphocyte proliferation and IL-2 production but enhanced IL-4 secretion in both diabetic and control groups. No changes in the levels of reduced glutathione and in the activities of catalase and SOD were observed in control T cells cultured in the presence of EPA and DHA. However, in diabetic patients, addition of n-3 PUFA to culture induced an increase in T cell levels of reduced glutathione and hydroperoxide, and in activities of catalase and SOD. Low levels of arachidonic acid (C20:4n-6) were found in plasma membrane phospholipids of lymphocytes from diabetic patients compared to controls. Incubation of lymphocytes with EPA and DHA was associated with an incorporation of these fatty acids in membrane phospholipids. In conclusion, the beneficial effects of n-3 PUFA on T cell functions in type I diabetes could be attributed to their suppressive action and modulation of cytokine secretion, and to the improvement of intracellular oxidative status.     

Evaluation-based closed-loop errors using principal component analysis and self-organisation map with an application to a pickling process

Closed-loop control is a basic technology in control engineering. Its role is to avoid the tracking error between set points and real variables. The evaluation of plant performance can be based on multivariate statistical process control connected to closed-loop errors behaviour. Due to its practicality, this approach has found many applications in several industries. This paper suggests a combined use of principal component analysis (PCA) and self-organisation map (SOM) algorithms to evaluate the process on the basis of closed-loop errors dynamic. Generally, it is possible to evaluate a product quality in the basis of the dynamic changes of the closed-loop control errors. In this paper, a new method based on the analysis of the control errors is proposed; it is carried out by a combined use of the PCA-SOM algorithm. Comparatively to the conventional PCA method, this new technique is characterised by the performant indexes that give an accurate evaluation of the process variability and its impact on the product quality. As shown in the different simulation results, the proposed approach gives a global evaluation and improves considerably the performance of computed indexes used for the evaluation of the controlled process.     

DFT study of conjugated biheterocyclic oligomers exhibiting a very low HOMO–LUMO energy gap

Density functional theory (DFT) is applied to study the structure and electronic properties of oligomers based on bithiophene bridged by a sp² carbon substituted by a chalcogen atom (O, S, Se and Te), and their polybifurane and polybipyrrole analogues. The important reduction of the energy gap which is observed for the whole series of biheterocyclic compounds, when going down the chalcogen group, is explained on the basis of an orbital interaction analysis. Bithiophene polymers bridged by a selenium or a tellurium substituted carbon atom are expected to exhibit very low energy band gaps.     

Polymer Ionomers for Rapid Prototyping and Rapid Manufacturing by Means of 3D Printing

Summary: The powder blend of poly(acrylic acid) (PAA) with zinc oxide or zinc oxide/magnesium oxide was applied successfully to produce zinc polycarboxylate during the 3D dispensing of an aqueous ink by means of 3D printers (Z402? from ZCorporation and Deskmodeler? from bmt Company). The layer‐by‐layer inkjet printing afforded zinc ionomer 3D objects with excellent water resistance, no inherent color formation and high mechanical and dimensional stabilities. In contrast to the 3D printing of conventional powders such as starch/cellulose/dextrose blends, poly(vinyl alcohol) (PVA) or plaster, no postprinting treatments were required. Excellent dimensional accuracy of the models, as evidenced by very small deviation of the dimensions from those of the corresponding CAD data, was achieved. The mechanical properties improved with increasing PAA content, ink amount (saturation value), decreasing particle size of the sintered zinc oxide ceramic. At high PAA content >7 wt.‐%, post‐treatment with aqueous zinc acetate solution improved the mechanical properties. The setting time of the zinc cements shows no significant effect on the mechanical properties, but on the water resistance of the models. The porosity of the 3D objects, measured by means of X‐ray microtomography (μ‐CT), had profound impact on the variations of the mechanical properties of the 3D objects prepared by 3D printing processes.

Comparison of three‐point‐bending tests of commercially available powders with selected zinc cements (ZC1, ZC2, ZC4, ZC19). Commercially available powders printed with recommended values of manufacturer. Zinc cements printed with saturation value 1.14 (Z402?).     

Adaptive support vector machine-based surface quality evaluation and temperature monitoring. Application to billet continuous casting process

A method for surface quality evaluation and temperature monitoring of the billet in continuous casting is considered in this paper. This method uses the difference between the measured and the filtered temperature computed using an adaptive support vector machine method. The temperature field, measured by an infrared camera, is affected by an important noise called calamine (a metal oxide generated during the cooling process). The quality of the billet’s surface temperature is connected to the secondary cooling behavior, and therefore an evaluation of the calamine effect is needed. Methods such as soft sensing and adaptive support vector machine are used for a global evaluation of calamine intensity on the monitored area of the billet in continuous casting. This kind of approaches is applied in continuous casting process for constructing a complementary condition monitoring system, which allows an online calamine evaluation. Simulation results, based on the measured surface temperature and the adaptive support vector machine analysis, showed that this new combined approach is easily implementable and gives good results when applied online.